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Born on 11 November 1596 in Rouen, France, she was baptised on 17 November 1596. At her birth, QueenElizabeth I of England sent a special ambassador who also proposed a new treaty between the two nations. Then, surprising everyone, Spain attacked Amiens. One of the first things Catherine Henriette's mother Gabrielle did was to ask the people of France to contribute financially to the war effort while she herself pawned her jewellery; in doing so she raised a substantial fortune.

In her youth, she was known as Mademoiselle de Vendôme, derived from the Duchy of Vendôme which had been in possession of the House of Bourbon since 1393. Her older brother, César, was legitimised in 1595 and given the title of Duke of Vendôme. César would later scheme against the crown against Cardinal Richelieu in the Fronde with their younger half-brother Gaston. Her youngest full sibling, Alexandre, was born in 1598 and died in 1629.

At the age of just three, her 26 year-old mother died of an attack of eclampsia after giving birth to a stillborn child. As a result of her mother's death, Catherine Henriette inherited her wealth in her own right. Her mother's duchy, Beaufort, was given to her older brother, César.

In 1610, her father was assassinated outside the Louvre Palace on 19 May. This left her eight year old half-brother Louis XIII the new king, with a regency under the power of his mother Marie de' Medici, who hated the royal bastards.

The dowry given to the House of Guise was the large sum of 1.3 million livres and included pensions as well. Most of this money was spent and re-mortgaged for various reasons including a failed lawsuit against her brother César.[1]

As Catherine Henriette was marrying into the House of Guise, she took on the style of Highness, the Guises being foreign princes at court. After her marriage, she was known as the Légitimée-duchesse. She used to sign documents as C H. L de France – Catherine Henriette. Légitimée de France.

Her marriage produced six children, three of whom would have issue. Her husband died in Paris at the Hôtel d'Elboeuf, the family town house. Catherine Henriette remained a widow for six years until her own death in 1663.